Different deformation mechanisms of two modified‐polystyrene bimodal systems

It is well known that the dominant toughening mechanism of rubber‐modified polystyrene is multiple crazing. Some researchers have investigated polystyrene that can be modified by rubbers with dual particle sizes, leading to better mechanical properties. That is, the way to absorb energy during the deformation process is crazing and cavitation induced by rubber particles. Two types of polybutadiene‐graft‐polystyrene (PB‐g‐PS) rubber modifiers which have core‐shell structures were synthesized via an emulsion graft polymerization using redox and oil‐soluble initiators, respectively. To balance the yield strength, general‐purpose polystyrene was blended with the PB‐g‐PS modifiers, as well as commercial high‐impact polystyrene. Blends were defined as R‐bimodal and O‐bimodal corresponding to dispersed PB‐g‐PS particles formed using the redox and oil‐soluble initiators, respectively. The impact strength of R‐bimodal was improved significantly by altering the ratio of core to shell. However, little change of impact strength was observed for O‐bimodal. Transmission electron microscopy images of fracture surfaces indicated that the deformation mechanism of R‐bimodal is shear‐yielding induced by multi‐crazing. Moreover, PB‐g‐PS particles dispersed in O‐bimodal can form a ‘cluster’ structure, leading to crazing to absorb energy. Scanning electron microscopy images also showed obvious distinctness between the R‐bimodal and O‐bimodal systems due to different deformation mechanisms. Copyright © 2010 Society of Chemical Industry     

Deformation mechanism of polystyrene toughened with sub‐micrometer monodisperse rubber particles

Core–shell polybutadiene‐graft‐polystyrene (PB‐g‐PS) rubber particles with different ratios of polybutadiene to polystyrene were prepared by emulsion polymerization through grafting styrene onto polybutadiene latex. The weight ratio of polybutadiene to polystyrene ranged from 50/50 to 90/10. These core‐shell rubber particles were then blended with polystyrene to prepare PS/PB‐g‐PS blends with a constant rubber content of 20 wt%. PB‐g‐PS particles with a lower PB/PS ratio (≤70/30) form a homogeneous dispersion in the polystyrene matrix, and the Izod notched impact strength of these blends is higher than that of commercial high‐impact polystyrene (HIPS). It is generally accepted that polystyrene can only be toughened effectively by 1–3 µm rubber particles through a toughening mechanism of multiple crazings. However, the experimental results show that polystyrene can actually be toughened by monodisperse sub‐micrometer rubber particles. Scanning electron micrographs of the fracture surface and stress‐whitening zone of blends with a PB/PS ratio of 70/30 in PB‐g‐PS copolymer reveal a novel toughening mechanism of modified polystyrene, which may be shear yielding of the matrix, promoted by cavitation. Subsequently, a compression‐induced activation method was explored to compare the PS/PB‐g‐PS blends with commercial HIPS, and the result show that the toughening mechanisms of the two samples are different. Copyright © 2006 Society of Chemical Industry     

Influence of core–shell rubber particles synthesized with different initiation systems on the impact toughness of modified polystyrene

Core–shell poly(butadiene‐graft‐styrene) (PB‐g‐PS) rubber particles were synthesized with different initiation systems by emulsion grafting polymerization. These initiation systems included the redox initiators and an oil‐soluble initiator, 1,2‐azobisisobutyronitrile (AIBN). Then the PB‐g‐PS impact modifiers were blended with polystyrene (PS) to prepare the PS/PB‐g‐PS blends. In the condition of the same tensile yield strength on both samples, the Izod test showed that the notched impact strength of PS/PB‐g‐PS(AIBN) was 237.8 J/m, almost 7 times than that of the PS/PB‐g‐PS(redox) blend, 37.2 J/m. From transmission electron microscope (TEM) photographs, using the redox initiators, some microphase PS zones existed in the core of PB rubber particles, which is called “internal‐grafting.” This grafting way was inefficient on toughening. However, using AIBN as initiator, a great scale of PS subinclusion was seen within the PB particle core, and this microstructure increased the effective volume fraction of the rubber phase with a result of improving the toughness of modified polystyrene. The dynamic mechanical analysis (DMA) on both samples showed that the glass transition temperature (T_g) of rubber phase of PS/PB‐g‐PS(AIBN) was lower than that of PS/PB‐g‐PS(redox). As a result, the PB‐g‐PS(AIBN) had better toughening efficiency on modified polystyrene than the PB‐g‐PS(redox), which accorded with the Kerner approximate equation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 738–744, 2007     

Morphology and mechanical properties of ABS blends prepared from emulsion‐polymerized PB‐g‐SAN impact modifier with AIBN as initiator

A series of PB‐g‐SAN impact modifiers (polybutadiene particles grafted by styrene and acrylonitrile) are synthesized by seed emulsion copolymerization initiated by oil‐soluble initiator, azobisiobutyronitrile (AIBN). The ABS blends are obtained by mixing SAN resin with PB‐g‐SAN impact modifiers. The mechanical behavior and the phase morphology of ABS blends are investigated. The graft degree (GD) and grafting efficiency (GE) are investigated, and the high GD shows that AIBN has a fine initiating ability in emulsion grafting of PB‐g‐SAN impact modifiers. The morphology of the rubber particles is observed by the transmission electron microscopy (TEM). The TEM photograph shows that the PB‐g‐SAN impact modifier initiated by AIBN is more likely to form subinclusion inside the rubber particles. The dynamic mechanical analysis on ABS blends shows that the subinclusion inside the rubber phase strongly influences the T_g, maximum tan δ, and the storage modulus of the rubber phase. The mechanical test indicates that the ABS blends, which have the small and uniform subinclusions dispersed in the rubber particles, have the maximum impact strength. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Controllable Synthesis of Submicrometer Core–Shell Modifier and Its Effect on Toughening Polypheylene Ether/Polystyrene Blends

Core–shell polybutadiene-graft-polystyrene (PB-g-PS) graft copolymers with different ratios of PB to PS are synthesized by emulsion polymerization. Further, the PB-g-PS copolymers are blended with polypheylene ether (PPE) and PS to prepare PPE/PS/PB-g-PS blends. The effects of PB-g-PS copolymer structure and matrix composition on the morphological, mechanical properties, and deformation mechanism of the blends are studied. The results show that the synthesized submicrometer-sized PB-g-PS copolymer has an excellent toughening efficiency, both the copolymer and PS are introduced into PPE resin to produce a ternary blend which is combined with high toughness and processing properties. The optimum toughening effect on PPE/PS matrix is observed at the core–shell weight ratio of 70/30 in PB-g-PS copolymer, and the impact strength of the blends increased from 101 to 550 J m⁻¹. In addition, the dispersion pattern of rubber particles in the matrix gradually changes from uniform dispersion to aggregation as the core–shell ratio of PB-g-PS copolymers increases. On the other hand, with the increase of PPE content, the dispersion of rubber particles in PPE/PS matrix is improved, and the deformation mechanism is changed from cracking to a combination of crazing and shear yielding, which can lead to absorb more energy to achieve better toughness.     

Toughening polystyrene by core–shell grafting copolymer polybutadiene-graft-polystyrene with potassium persulfate as initiator

Core–shell polybutadiene-graft-polystyrene rubber particles with different ratios of polybutadiene core to polystyrene shell were synthesized by an emulsion polymerization using K₂S₂O₈ as an initiator. Then the core–shell rubber particles were blended with PS to prepare PS/PB-g-PS. The rubber particles with a size of 0.3–0.5 μm could toughen polystyrene significantly. The mechanical properties, morphologies and deformation mechanisms of samples were extensively investigated. The experimental results showed that the dispersion of rubber particles in a “cluster” state leads to better impact resistances. Crazing occurred from rubber particles and extended in a bridge-like manner to neighboring rubber particles parallel to the equatorial direction.     

Environmentally responsive amphiphilic cationic block copolymers synthesized by 2,2,6,6‐Tetramethylpiperidinyloxy mediated living free‐radical polymerization

Polychloromethylstyrene (PCMS)‐block‐polystyrene (PS) copolymers were prepared by controlled free‐radical polymerization in the presence of 2,2,6,6‐tetramethylpiperidinooxy and 2,2′‐azobisisobutyronitrile (AIBN) initiator. The PCMS‐b‐PS copolymers had narrow molecular weight distributions, and the block lengths were controlled by the reaction time and the molar ratios of chloromethylstyrene/AIBN and styrene/PCMS macroinitiator. The block copolymers were further quaternized with triethylamine. The amphiphilic cationic block copolymers formed colloidal particles; the effects of the pH value, salt concentration, and solvent polarity on the particle size were investigated with a dynamic light scattering analyzer. The average colloid size increased with increasing pH value and salt concentration. This implied that the colloid formed a protonated hydrophilic shell and hydrophobic styrene core in water. Furthermore, with the addition of tetrahydrofuran to the aqueous solution, the styrene segments in the core could be inverted to the outside of the colloid. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

ABS modified with hydrogenated polystyrene‐grafted‐natural rubber

Natural rubber (NR) latex was grafted by emulsion polymerization with styrene monomer, using cumene hydroperoxide/tetraethylene pentamene as redox initiator system. The polystyrene‐grafted NR (PS‐g‐NR) was hydrogenated by diimide reduction in the latex form using hydrazine and hydrogen peroxide with boric acid as a promoter. At the optimum condition for graft copolymerization, a grafting efficiency of 81.5% was obtained. In addition, the highest hydrogenation level of 47.2% was achieved using a hydrazine:hydrogen peroxide molar ratio of 1:1.1. Hydrogenation of the PS‐g‐NR (H(PS‐g‐NR)) increased the thermal stability. Transmission electron microscopy analysis of the H(PS‐g‐NR) particles revealed a nonhydrogenated rubber core and hydrogenated outer rubber layer, in accordance with the layer model. The addition of H(PS‐g‐NR) at 10 wt % as modifier in an acrylonitrile–butadiene–styrene (ABS) copolymer increased the tensile and impact strengths and the thermal resistance of the ABS blends, and to a greater extent than that provided by blending with NR or PS‐g‐NR. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Toughening of epoxy thermosets with polystyrene‐block‐polybutadiene‐block‐ polystyrene triblock copolymer via formation of nanostructures

In this contribution, we reported to utilize polystyrene‐block‐polybutadiene‐block‐polystyrene (PS‐b‐PB‐b‐PS), a commercial triblock copolymer to toughen epoxy thermosets. First, a PS‐b‐PB‐b‐PS triblock copolymer was chemically modified with hydroboration‐oxidation reaction, with which the midblock was hydroxylated whereas the endblocks remained unaffected. It was found that the degree of hydroxylation was well controlled. One of the hydroxylated PS‐b‐PB‐b‐PS samples was then used as the macromolecular initiator to synthesize a poly(ε‐caprolactone)‐grafted PS‐b‐PB‐b‐PS via the ring‐opening polymerization. It was found that the PS‐b‐PB‐b‐PS with poly(ε‐caprolactone) grafts can be successfully employed to nanostructure epoxy thermosets; the “core‐shell” microdomains composed of PB and PS were generated in the nanostructured thermosets. The nanostructured thermosets displayed improved fracture toughness. POLYM. ENG. SCI., 59:2387–2396, 2019. © 2019 Society of Plastics Engineers     

核壳结构微纳橡胶粒子的可控合成及对PPO/PS共混体系的增韧

采用乳液聚合方法在粒径为100 nm的聚丁二烯(PB)胶乳上接枝聚合苯乙烯(St),合成了核壳比为70/30(PB/PS)的PB-g-PS接枝共聚物,将其与聚苯醚(PPO)、聚苯乙烯(PS)树脂熔融共混,制备出一系列橡胶含量、基体组成不同的PPO/PS/PB-g-PS共混物,并考察了共混物的相容性、力学性能及形态结构。结果发现:PPO与PS为完全相容体系,且PB-g-PS在PPO/PS基体中的均匀分散程度随体系中PPO引入量的增大而明显改善,共混物的冲击强度及屈服强度也随之逐渐增大,进而促使共混物发生脆-韧转变所需的橡胶含量逐渐降低;随着共混体系中橡胶含量的增加,共混物的冲击强度逐渐提高,而屈服强度却逐渐降低,共混物的韧性断裂特征越发显著。     

种子聚合法制备PS/PAA核壳微球的研究

设计制备了以疏水性聚苯乙烯(PS)为核、以亲水性聚丙烯酸(PAA)为壳的PS/PAA核壳结构复合微球。首先利用无皂乳液聚合法制备了亚微米级的PS微球,再以其为种子,利用种子无皂乳液聚合法制备PS/PAA核壳微球。在种子聚合阶段,选用AIBN当引发剂,经过红外光谱(IR)表征,表明当使用油溶性引发剂偶氮二异丁腈(AIBN),使其最终形成PS/PAA核壳结构微球。这种方法解决了亲水性较强的单体在以水为介质时在PS微球溶于少量的苯乙烯(St),并在引发聚合之前经过充分的吸附溶胀,可使亲水性单体AAc在PS种子微球表面聚合生成壳层,解决表面不容易直接聚合生成壳层的问题。     

Molecular simulation of the effect of graft structure on the miscibility of high‐impact polystyrene blends

High‐impact polystyrene (HIPS) is a kind of thermoplastic with good impact, which is considered to derive from the biphase of microstructure studied with SEM, etc. In this article, the influence of polystyrene (PS)/polybutadiene (PB) graft structure to the behavior of HIPS was studied through molecular simulation. The analysis of Flory‐Huggis parameter χ and radial distribution function (RDF) shows that the blend system of PS/PB has the best miscibility when the mass ratio of PS/PB is 60/40. In the toughening process, however, the graft copolymer PB‐g‐S is formed. For the PS/PB‐g‐S system with the same repeat unit of PS, PB‐g‐S chains with two grafts [PB‐g‐S(G = 2)] are better than PB‐g‐S chains with one graft [PB‐g‐S(G = 1)] in miscibility, which is in accord with the study of Fischer and Hellmann. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Synthesis and application of poly(butadiene-g-acrylonitrile–styrene) core–shell rubber particles for use in epoxy resin toughening. I. Synthesis of poly(butadiene-g-acrylonitrile–styrene)

Graft copolymers of acrylonitrile (AN)–styrene (ST) onto polybutadiene were prepared via emulsion polymerization method using a redox initiator system, cumene hydroperoxide–tetrasodium pyrophosphate–ferrous sulfate–dextrose. The effects of initiator, reaction temperature, reaction time, polymer/grafting monomer ratio, and monomer dropping frequency on the graft copolymerization reaction were investigated. Transmission electron micrographs confirmed that the synthesized particles had a core–shell shaped structure. The powdery core–shell shaped poly(butadiene-g-AN–ST) particles with various AN contents in their shells and with different shell thicknesses were prepared, which can be incorporated into brittle epoxy resin as impact modifier. © 1996 John Wiley & Sons, Inc.     

Synthesis of polypropylene graft copolymers from a hydroxyl‐groups‐containing polypropylene precursor via atom‐transfer radical polymerization

Isotactic polypropylene graft copolymers, isotactic[polypropylene‐graft‐poly(methyl methacrylate)] (i‐PP‐g‐PMMA) and isotactic[polypropylene‐graft‐polystyrene] (i‐PP‐g‐PS), were prepared by atom‐transfer radical polymerization (ATRP) using a 2‐bromopropionic ester macro‐initiator from functional polypropylene‐containing hydroxyl groups. This kind of functionalized propylene can be obtained by copolymerization of propylene and borane monomer using isospecific MgCl₂‐supported TiCl₄ as catalyst. Both the graft density and the molecular weights of i‐PP‐based graft copolymers were controlled by changing the hydroxyl group contents of functionalized polypropylene and the amount of monomer used in the grafting reaction. The effect of i‐PP‐g‐PS graft copolymer on PP‐PS blends and that of i‐PP‐g‐PMMA graft copolymer on PP‐PMMA blends were studied by scanning electron microscopy. Copyright © 2006 Society of Chemical Industry     

Use of natural rubber‐g‐polystyrene as a compatibilizer in casting natural rubber/polystyrene blend films

Natural rubber/polystyrene (NR/PS) blend films with weight ratios of 70/30, 60/40, and 50/50 were prepared using polystyrene grafted natural rubber copolymers (NR‐g‐PS) as the compatibilizer. Copolymers with molar ratios of 90/10, 80/20, and 70/30 were synthesized via emulsion copolymerization using tert‐butyl hydroperoxide/tetraethylene pentamine as an initiator. The copolymers were subsequently added into the blends at 0, 5, 10, 15, 20, 25, and 30 phr. The mixtures were cast into films by the solution‐casting method using toluene as the casting solvent. Mechanical and morphological properties of the prepared films were investigated. The film prepared from 80/20 NR‐g‐PS showed higher tensile and tear strength, as well as finer domain size of the dispersed phase, than those prepared from 90/10 and 70/30 NR‐g‐PS. However, the mechanical properties of the films were decreased at high loading of the copolymers. In addition, themogravimetric analysis revealed that weight loss was decreased upon introduction of the compatibilizer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 826–831, 2005     

Effects of the polybutadiene/poly(styrene‐co‐acrylonitrile) ratio in a polybutadiene‐g‐poly(styrene‐co‐acrylonitrile) impact modifier on the morphology and mechanical behavior of acrylonitrile–butadiene–styrene blends

Polybutadiene‐g‐poly(styrene‐co‐acrylonitrile) (PB‐g‐SAN) impact modifiers with different polybutadiene (PB)/poly(styrene‐co‐acrylonitrile) (SAN) ratios ranging from 20.5/79.5 to 82.7/17.3 were synthesized by seeded emulsion polymerization. Acrylonitrile–butadiene–styrene (ABS) blends with a constant rubber concentration of 15 wt % were prepared by the blending of these PB‐g‐SAN copolymers and SAN resin. The influence of the PB/SAN ratio in the PB‐g‐SAN impact modifier on the mechanical behavior and phase morphology of ABS blends was investigated. The mechanical tests showed that the impact strength and yield strength of the ABS blends had their maximum values as the PB/SAN ratio in the PB‐g‐SAN copolymer increased. A dynamic mechanical analysis of the ABS blends showed that the glass‐transition temperature of the rubbery phase shifted to a lower temperature, the maximum loss peak height of the rubbery phase increased and then decreased, and the storage modulus of the ABS blends increased with an increase in the PB/SAN ratio in the PB‐g‐SAN impact modifier. The morphological results of the ABS blends showed that the dispersion of rubber particle in the matrix and its internal structure were influenced by the PB/SAN ratio in the PB‐g‐SAN impact modifiers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2165–2171, 2005     

Fractographic analysis of the crack resistance of styrene–acrylonitrile/polybutadiene‐g‐styrene–acrylonitrile blends as evaluated by the essential work of fracture method

The fracture surfaces and deformation micromechanisms of styrene‐co‐acrylonitrile (SAN)/polybutadiene‐g‐styrene‐co‐acrylonitrile (PB‐g‐SAN) blends with the compositions ranging from 65/35 to 0/100 were studied with a scanning electron microscopy technique. The results were compared to the essential work of fracture parameters obtained in a previous study conducted on double‐edge notched tension specimens. Different plastic damage mechanisms were observed, and they depended on the blend composition. For blends of 65/35 and 45/55, a high degree of rubber particle cavitation and multiple cracking followed by the massive shear yielding of the matrix were found to be the main source of energy dissipation during crack growth. Within this compositional range, more intense plastic damage in a larger volume of material, especially at the notched region, was observed as the concentration of the rubbery phase increased. For the 25/75 blend, the prevailing mechanism was pure shear yielding without any sign of cavitation inside the particles, and the fracture surface became relatively flat and was covered with aligned small microcracks. This sample showed the highest specific essential work (w_e) value among the blends examined in the previous study. For the samples containing concentrations of dispersed phase higher than 75%, the shear yielding process gradually became less important with the progressive importance of multiple crazing so that high‐magnification micrographs revealed extensive microcracking/crazing both inside and between the rubber particles, as the only active deformation micromechanism for neat PB‐g‐SAN. The variation w_e and specific plastic work of fracture with the PB‐g‐SAN phase content were successfully explained in terms of prevalent deformation mechanisms. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40072.     

Mechanical properties and deformation behaviors of acrylonitrile‐butadiene‐styrene under Izod impact test and uniaxial tension at various strain rates

Two polybutadiene‐graft‐acrylonitrile‐styrene copolymer (PBD‐g‐SAN) impact modifiers with different rubber particle size were synthesized by seeded emulsion polymerization. Acrylonitrile‐butadiene‐styrene (ABS) blends with a constant rubber concentration of 15 wt% were prepared by blending those impact modifiers and SAN resin. The major focus was the mechanical properties and deformation mechanisms of ABS blends under Izod impact test and uniaxial tension at various strain rates from 2.564 × 10^?4 S^?1 upto 1.282 × 10^?1 S^?1. By the combination of transmission electron microscope and scanning electron microscope, it was concluded that crazes and cavitation coexisted in ABS blends. The deformation mechanisms of ABS blend containing large rubber particles was rubber particles cavitation and shear yielding in the matrix including crazes, and they do not change with the strain rate. Different from ABS blend with large rubber particles, deformation mechanism of ABS with small rubber particles under tensile condition was only involved in shear yielding in the matrix and no crazes were formed. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Natural rubber‐g‐methyl methacrylate/poly(methyl methacrylate) blends

The grafting of the methyl methacrylate (MMA) monomer onto natural rubber using potassium persulfate as an initiator was carried out by emulsion polymerization. The rubber macroradicals reacted with MMA to form graft copolymers. The morphology of grafted natural rubber (GNR) was determined by transmission electron microscopy and it was confirmed that the graft copolymerization was a surface‐controlled process. The effects of the initiator concentration, reaction temperature, monomer concentration, and reaction time on the monomer conversion and grafting efficiency were investigated. The grafting efficiency of the GNR was determined by a solvent‐extraction technique. The natural rubber‐g‐methyl methacrylate/poly(methyl methacrylate) (NR‐g‐MMA/PMMA) blends were prepared by a melt‐mixing system. The mechanical properties and the fracture behavior of GNR/PMMA blends were evaluated as a function of the graft copolymer composition and the blend ratio. The tensile strength, tear strength, and hardness increased with an increase in PMMA content. The tensile fracture surface examined by scanning electron microscopy disclosed that the graft copolymer acted as an interfacial agent and gave a good adhesion between the two phases of the compatibilized blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 428–439, 2001     

Preparation of monodispersed and lipophilic attapulgite and polystyrene nanorods via surface‐initiated atom transfer radical polymerization

A new kind of initiator, 3‐(2‐bromo‐2‐methylacryloxy)propyltriethysiliane (MPTS‐Br), was prepared with a simply hydrobrominated commercial silane coupling agent (3‐methacryloxy‐proplytriethysilane, MPTS). It has been one‐step self‐assemble onto the surface of attapulgite (ATP) nanorods in the dispersion system, and by using this initiator‐modified nanorod (MPTS‐Br‐modified ATP nanoparticles, ATP‐MPTS‐Br) as macroinitiator for atom transfer radical polymerization (ATRP). Structurally well‐defined homopolymer polystyrene (PS) and block polymer poly(styrene‐b‐methyl methacrylate) (PS‐b‐PMMA) chains were then grown from the needle‐shaped nanorods surface to yield monodispersed nanorods composed of ATP core and thick‐coated polymer shell (ATP and PS). The graft polymerization parameters exhibited the characteristics of a controlled/”living” polymerization. The PS‐grafted ATP nanorods could be dispersed well in organic solvent with nanoscale. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011